2-alkyl-4-methoxy-5-aminophenol or salt thereof, or 2-alkyl-4-methoxy-5-substituted aminophenol or salt thereof, and dyeing composition for keratin fibers comprising the same

ABSTRACT

A 2-alkyl-4-methoxy-5-aminophenol or a salt thereof; a 2-alkyl-4-methoxy-5-nitrophenol or 2-alkyl-4-methoxy-5-nitrophenyl mesylate, each an intermediate in the preparation of the 2-alkyl-4-methoxy-5-aminophenol; and a dyeing composition for keratin fibers comprising a color-developing material and the 2-alkyl-4-methoxy-5-aminophenol or the salt thereof as a coupling agent are disclosed. 
     Further, a 2-alkyl-4-methoxy-5-substituted aminophenol or a salt thereof; a 2-alkyl-4-methoxy-5-substituted aminophenol derivative, whcih is an intermediate in the preparation of the 2-alkyl-4-methoxy-5-substituted aminophenol; and a dyeing composition for keratin fibers comprising a color-developing material and the 2-alkyl-4-methoxy-5-substituted aminophenol or the salt thereof as a coupling agent are disclosed.

FIELD OF THE INVENTION

This invention relates to a novel 2-alkyl-4-methoxy-5-aminophenol or asalt thereof, a dyeing composition for keratin fibers comprising thesame, and a novel derivative thereof, which is an intermediate in thepreparation of the 2-alkyl-4-methoxy-5-aminophenol.

The present invention further relates to a novel2-alkyl-4-methoxy-5-substituted aminophenol, a dyeing composition forkeratin fibers comprising the same, and a novel derivative thereof,which is an intermediate in the preparation of the2-alkyl-4-methoxy-5-substituted aminophenol.

BACKGROUND OF THE INVENTION

So-called oxidation dyes, wherein a color-developing material iscombined with a coupling agent, have been widely used in dyeing keratinfibers such as the hair. In the case of such an oxidation dye, aso-called oxidation pigment, which has been formed by the oxidationcoupling of a color-developing material with a coupling agent, wouldintensely dye, for example, the hair.

Known examples of the color-developing material includep-phenylenediamine derivatives, p-aminophenol derviatives,diaminopyridine derivatives, 4-aminopyrazolone derivatives andheterocyclic hydrazone derivatives; while known examples of the couplingagent include α-naphthol, o-cresol, m-cresol, 2,6-dimethylphenol,2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol,benzcatechin, pyrogallol, 1,5-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 5-amino-2-methylphenol, hydroquinone,2,4-diaminoanisole, m-toluylenediamine, 4-aminophenol, resorcin,resorcin monomethyl ether, m-phenylenediamine,1-phenyl-3-methyl-5-pyrazolone, 1-phenyl-3-amino-5-pyrazolone,1-phenyl-3,5-diketopyrazolidine,1-methyl-7-dimethylamino-4-hydroxyquinolone-2,1-amino-3-acetylacetamino-4-nitrobenzene,1-amino-3-cyanoacetylamino-4-nitro-benzene, m-aminophenol,4-chlororesorcin, 2-methylresorcin, 2,4-diaminophenoxyethanol,2,6-diaminopyridine, 3,5-diamino-trifluoromethylbenzene,2,4-diaminofluorobenzene, 3,5-diaminofluorobenzene,2,4-diamino-6-hydroxypyrimidine, 2,4,6-triaminopyrimidine,2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine,4,6-diamino-2-hydroxypyrimidine, p-nitro-o-phenylenediamine,2-amino-5-nitrophenol, p-nitro-m-phenylenediamine,o-nitro-p-phenylenediamine and 2-amino-4-nitrophenol.

However known oxidation dyes are unsatisfactory in chroma, dyeabilitypower and fastness. Since these properties largely depend on theproperties of the employed coupling agents, it is highly important inthe preparation of an excellent oxidation dye to find out a materialwhich is excellent as a coupling agent.

SUMMARY OF THE INVENTION

Under these circumstances, we have synthesized a number of compounds andexamined their properties as a coupling agent. As a result, we havefound out that a 2-alkyl-4-methoxy-5-aminophenol represented by formula(I) below or a salt thereof, or a 2-alkyl-4-methoxy-5-substitutedaminophenol represented by formula (III) below or a salt thereof isexcellent from the viewpoint of the above-mentioned properties, thuscompleting the present invention.

Accordingly, the present invention provides a2-alkyl-4-methoxy-5-aminophenol represented by formula (I) below or asalt thereof: ##STR1## wherein R¹ represents a substituted orunsubstituted lower alkyl group; and a 2-alkyl-4-methoxy-5-nitrophenylmesylate or 2-alkyl-4-methoxy-5-nitrophenol represented by formula (II)below, each an intermediate in the preparation of the compound offormula (I) above: ##STR2## wherein R¹ represents a substituted orunsubstituted lower alkyl group; and R² represents a hydrogen atom ormesyl group.

The present invention further provides a dyeing composition for keratinfibers comprising the compound represented by formula (I) as a couplingagent.

The present invention furthermore provides a2-alkyl-4-methoxy-5-substituted aminophenol represented by formula (III)below or a salt thereof: ##STR3## wherein R¹ represents a substituted orunsubstituted lower alkyl group; R³ represents a hydrogen atom, asubstituted or unsubstituted lower alkyl group or a substituted orunsubstituted hydroxyalkyl group; and R⁴ represents a substituted orunsubstituted lower alkyl group, a substituted or unsubstituted mono- ordi-hyroxyalkyl group, a substituted or unsubstituted acetyl group, asubstituted or unsubstituted benzoyl group, or mesyl group.

The present invention still provides a novel2-alkyl-4-methoxy-5-substituted aminophenol derivative represented byformula (IV) or (V): ##STR4## wherein R¹ represents a substituted orunsubstituted lower alkyl group; and R⁴ and R^(4'), which may be thesame or different, each represents a substituted or unsubstituted loweralkyl group, a substituted or unsubstituted hydroxyalkyl group, asubstituted or unsubstituted acetyl group, a substituted orunsubstituted benzoyl group, or mesyl group; and ##STR5## wherein R¹represents a substituted or unsubstituted lower alkyl group and n is aninteger of 2 to 4; each which is an intermediate in the preparation ofthe compound of formula (III) above.

The present invention still further provides a dyeing composition forkeratin fibers comprising the compound represented by formula (III) as acoupling agent.

DETAILED DESCRIPTION OF THE INVENTION

The definitions for R¹, R², R³ and R⁴ in formulae from (I) through (V)above are explained below in more detail.

Examples of the substituted or unsubstituted lower alkyl group includethe alkyl groups having 1 to 5 carbon atoms, preferably 1 to 3 carbonatoms, and the examples of the substituent which may substitute thereforinclude alkyl group, hydroxyalkyl group, the group of --CH₂)_(m)--O--CH₂)_(m) --OH wherein m is an integer of 1 to 5, and the like.Specific Examples the substituted or unsubstituted lower alkyl groupinclude methyl, ethyl, propyl, iso-propyl and t-butyl. Among them,methyl, and ethyl are preferred.

Examples of the substituted or unsubstituted hydroxyalkyl group includethe ones in which an alkyl moiety thereof contain 2 to 10 carbon atoms,preferably 2 to 3 carbon atoms and contain 1 to 3, preferably 1 to 2hydroxy group(s), and the examples of the substituent which maysubstitute therefor include methyl, ethyl, propyl, and the like. Thehydroxy group(s) is preferably contained in the hydroxyalkyl group at β-or γ-position. Specific examples of the substituted or unsubstitutedhydroxyalkyl group include 2-hydroxyethyl, 2-hydroxypropyl,2,3-dihydroxypropyl and 3-hydroxypropyl. Among them, 2-hydroxyethyl and2-hydroxypropyl are preferred.

Examples of the substituent which may substitute for acetyl groupinclude fluorine atom, chlorine atom, methyl and ethyl. Specificexamples of the substituted or unsubstituted acetyl group includeacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, chloroacetyl,dichloroacetyl, trichloroacetyl and propyonyl. Among them, acetyl,fluoroacetyl, difluoroacetyl and trifluoroacetyl are preferred.

Examples of the substituted or unsubstituted benzoyl group include theones having 7 to 15 carbon atoms, preferably 7 to 10 carbon atoms, andexamples of the substituent therefor include methyl, t-butyl, nitro andchlorine. Specific examples thereof include benzoyl, toluoyl,m-nitrobenzoyl and chlorobenzoyl. Among them, benzoyl and toluoyl arepreferred.

Specific examples of the 2-alkyl-4-methoxy-5-aminophenol compoundrepresented by formula (I) and the 2-alkyl-4-methoxy-5-substitutedaminophenol compound represented by formula (III), each according to thepresent invention, will be mentioned below. However, the presentinvention is not construed to be restricted thereby.

Examples of the 2-alkyl-4-methoxy-5-aminophenol compound represented byformula (I) include 2-methyl-4-methoxy-5-aminophenol2-ethyl-4-methoxy-5-aminophenol, 2-propyl-4-methoxy-5-aminophenol and2-t-butyl-4-methoxy-5-aminophenol.

Examples of 2-alkyl-4-methoxy-5-substituted aminophenol compoundrepresented by formula (III) include2-methyl-4-methoxy-5-methylaminophenol,2-methyl-4-methoxy-5-ethylaminophenol,2-methyl-4-methoxy-5-mesylaminophenol,2-methyl-4-methoxy-5-dimethylaminophenol,2-methyl-4-methoxy-5-diethylaminophenol,2-methyl-4-methoxy-5-benzoylaminophenol,2-methyl-4-methoxy-5-acetylaminophenol,2-methyl-4-methoxy-5-(fluoroacetyl)aminophenol,2-methyl-4-methoxy-5-(difluoroacetyl)aminophenol,2-methyl-4-methoxy-5-(trifluoroacetyl)aminophenol,2-methyl-4-methoxy-5-(2-hydroxyethyl)aminophenol,2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenol, and2-methyl-4-methoxy-5-bis(2-hydroxypropyl)aminophenol.

The 2-alkyl-4-methoxy-5-aminophenol of the formula (I) of the presentinvention may be prepared by, for example, methylating a2-alkyl-4-hydroxy-5-nitrophenyl mesylate of formula (VI) to thereby givea compound of formula (IIa), demesylating the compound of formula (IIa)to thereby give a compound of (VII) and then reducing the compound offormula (VII), in accordance with the following reaction scheme:##STR6##

The starting compound of formula (VI) may be easily prepared inaccordance with a manner as described, for example, in Japan Kokai No.62-240960.

The starting compound of formula (VI) may be methylated by commonmethods for methylating phenols. Among these methods, the dimethylsulfate method is convenient and effective. The demesylation of thecompound (IIa) may be preferably conducted in an alkali. The compound(VII) may be reduced by a common method for reducing a nitro group.Catalytic hydrogenation or reduction with an aqueous solution of aceticacid/iron is convenient and effective. In the catalytic hydrogenation,palladium, platinum, copper or nickel may be used as a catalyst. As asolvent therefor, methanol, ethanol, ethyl acetate or dimethylformamidemay be selected. The reaction may be conducted at a temperature rangingfrom room temperature to the boiling point of the solvent selected. Thehydrogen gas pressure may range from 1 to 250 kg/cm². After thecompletion of the reduction, the catalyst is removed by filtration.After concentration, the filtrate may be easily purified by distillationor recrystallization. The reduction with an aqueous solution of aceticacid/iron may be conducted by adding a solvent miscible with the aqueoussolution of acetic acid, for example, methanol, ethanol, acetone,N,N-dimethylformamide, if required, and heating the obtained mixtureunder reflux in the presence of excessive iron. After the completion ofthe reaction, the solid matters are filtered off. After extracting withan appropriate organic solvent, the filtrate may be easily purified bydistillation or recrystallization.

The 2-alkyl-4-methoxy-5-substituted aminophenol of formula (III) of thepresent invention may be prepared by, for example, introducingsubstituent(s) to the amino group of the compound represented by formula(I) above in conventional manners.

For example, the 2-alkyl-4-methoxy-5-substituted aminophenol of formula(IIIa) below may be prepared by diacetylating or dimesylating a2-alkyl-4-methoxy-5-aminophenol of formula (I) to give a compound (IV)and then selectively eliminating the O-acetyl group or O-mesyl group, inaccordance with the following reaction scheme: ##STR7## wherein R¹, R⁴and R^(4') are defined as above.

Further, for example, the 2-alkyl-4-methoxy-5-substituted aminophenol offormula (IIIb) below may be prepared by acylating a2-alkyl-4-methoxy-5-aminophenol of formula (I) above with β-chloroethylchloroformate to give compound (VIII), and then conducting cyclizationto give 1,3oxazolidin-2-one (Va), followed by hydrolysis thereof toobtain 2-alkyl-4-methoxy-5-(2-hydroxyethyl)aminophenol, in accordancewith the following reaction scheme. ##STR8## wherein R¹ is defined asabove.

Each of the compound of formula (I) or (III) of the present inventionmay be converted into a salt of an organic or inorganic acid (forexample, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid,propionic acid, lactic acid, citric acid) to thereby improve theworkability during the formulation.

When the compound of formula (I) or (III) of the present invention isused as a coupling agent together with a known color-developmentmaterial, a dyeing composition for keratin fibers showing a wide rangeof color tone (yellow to red to blue) can be obtained.

As the color-developing material to be used in the present invention,those commonly employed in oxidation hair dyes may be selected. Examplesthereof include p-phenylene-diamine derivatives such asp-phenylenediamine, toluene-2,5-diamine, N-phenyl-p-phenylenediamine and2-chloro-p-phenylenediamine; p-aminophenol derivatives such asp-aminophenol, 5-aminosalicylic acid and 2,4-diaminophenol; pyridinederivatives such as 2,5-diaminopyridine and 2,3-diaminopyridine; andpyrimidine derivatives such as tetraaminopyrimidine.

Among these color-developing materials, p-aminophenol derivativesrepresented by formula (IX) below are preferred in combination with thecompound of formula (I) or with the compound of formula (III) in whichR⁴ is a hydroxyalkyl group: ##STR9## wherein X represents hydrogen atom,a halogen atom, carboxyl group or acetylamino group; to obtain a reddishcolor tone of an extremely high chroma and a high fastness. Examples ofthe compound of formula (XI) include p-aminophenol, 5-aminosalicylicacid, 3-carboxyl-4-aminophenol, 2-acetylamino-4-aminophenol and2-chloro-4-aminophenol.

On the other hand, p-phenylenediamine derivatives represented by formula(X) are preferred in combination with the compound of formula (III) inwhich R⁴ is acetyl group or mesyl group: ##STR10## wherein R⁵ representsa hydrogen atom, a chlorine atom, methyl group hydroxyethyl group orβ-hydroxyethoxy group; to obtain a bluish color tone of an extremelyhigh chroma and a high fastness.

The dyeing composition of the present invention may comprise othercoupling agent(s). In some cases, it is also possible to add asubstantive dye to the dyeing composition of the present invention so asto additionally change the color. Examples of such a substantive dyeinclude those specified as Standard Dyeing Materials published by JapanHair Color Association, such as 2-amino-4-nitrophenol,2-amino-5-nitrophenol, nitro-p-phenylenediamine hydrochloride,nitro-p-phenylenediamine, p-aminophenylsulfamic acid,p-nitro-o-phenylenediamine, picramic acid, sodium picramate, picricacid, chrome brown RH, hematein, nitro-p-phenylenediamine sulfate,p-nitro-o-phenylenediamine sulfate, p-nitro-m-phenylenediamine sulfate,1-amino-4-methylaminoanthraquinone and 1,4-diaminoanthraquinone; aciddyes such as Red No. 2, Red No. 3, Red No. 102, Red No. 104, Red No.105, Red No. 106, Yellow No. 4, Yellow No. 5, Green No. 3, Blue No. 1,Blue No. 2, Red No. 201, Red No. 227, Red No. 230, Red No. 231, Red No.232, Orange No. 205, Orange No. 207, Yellow No. 202, Yellow No. 203,Green No. 201, Green No. 204, Green No. 205, Blue No. 202, Blue No. 203,Blue No. 205, Brown No. 201, Red No. 401, Red No. 502, Red No. 503, RedNo. 504, Red No. 506, Orange No. 402, Yellow No. 402, Yellow No. 403 ,Yellow No. 406, Yellow No. 407, Green No. 401, Green No. 402, Purple No.401 and Black No. 401; oil-soluble dyes such as Red No. 215, Red No.218, Red No. 225, Orange No. 201, Orange No. 206, Yellow No. 201, YellowNo. 204, Green No. 202, Purple No. 201, Red No. 501, Red No. 505, OrangeNo. 403, Yellow No. 404, Yellow No. 405 and Blue No. 403; basic dyessuch as Red No. 213 and Red No. 214; and basic dyes manufactured byArianor Co. such as Sienna Brown, Mahogany, Madder Red, Steel Blue andStraw Yellow. Among these dyes, nitrophenylenediamine, nitro-aminophenoland anthraquinone are preferable.

The dyeing composition of the present invention may (auto) oxidizedcoupling with oxygen in the atmosphere so as to dye, for example, thehair. However it is preferable to induce the oxidation coupling byadding a chemical oxidizing agent thereto. Examples of particularlypreferable oxidizing agents include hydrogen peroxide; products obtainedby adding hydrogen peroxide to urea, melamine or sodium borate; andmixtures of such a hydrogen peroxide adduct with potassium peroxidedisulfate.

The dyeing composition of the present invention may be preferablyprovided in the form of, for example, cream, emulsion, gel, solution.The dyeing composition of the present invention may be formulated intosuch a form by adding various additives commonly employed in the fieldof cosmetics (for example, wetting agent (emulsifier), solubilizer,thickener, stabilizer, texture improver, hair styling base, perfume) tothe above-mentioned color-developing material and coupling agent andprocessing the obtained mixture in a conventional manner. Examples ofthe wetting agent (emulsifier) which can be used in the presentinvention include alkyl benzenesulfonates, fatty alcohol sulfates, alkylsulfonates, fatty acid alkanol amides and adducts of ethylene oxide tofatty alcohols. Examples of the thickener include methyl cellulose,starch, higher fatty alcohol, paraffin oil and fatty acids. Examples ofthe stabilizer include reducing agents such as sulfites, andhydroquinone derivatives and chelating agents. Examples of the textureimprover and the hair styling base include silicone, higher alcohols,oils such as various nonionic surfactants and various cationic polymers.

These compositions may contain the color-developing material and thecoupling agent in an amount in total of from 0.2 to 10% (by weight basedon the total weight of the composition, the same will applyhereinafter), preferably from 1 to 5%. The wetting agent (emulsifier)and the thickener may be usually used respectively in amounts of from0.5 to 30% and from 0.1 to 25%.

It is preferable that the pH value of the total composition is adjustedto pH of from 8 to 10.

Keratin fibers may be dyed with the dyeing composition of the presentinvention, for example, in the following manner. First, an oxidizingagent is added to the dyeing composition of the present invention so asto induce oxidation coupling. The dyeing solution thus obtained isapplied to the keratin fibers. After allowing to stand for 10 to 50minutes, preferably 25 to 35 minutes, the keratin fibers are washed andthen dried. The application of the dyeing solution may be conducted atfrom 15° to 40° C.

As described above, the use of the 2-alkyl-4-methoxy-5-substitutedaminophenol of the present invention or a salt thereof, or the2-alkyl-4-methoxy-5-substituted aminophenol or a salt thereof in adyeing composition for keratin fibers comprising a color-developingmaterial and a coupling agent makes it possible to dye keratin fibersover a wide range of color tone. The color tone thus obtained isexcellent in chroma, dyeability power and fastness. When the2-alkyl-4-methoxy-5-aminophenol of formula (I) or2-alkyl-4-methoxy-5-substituted aminophenol of formula (III) in which R⁴is a hydroxyalkyl group, is combined with a p-aminophenol derivativewhich is used as a color-developing material, a reddish color tone of anextremely high chroma and a high fastness can be obtained.Alternatively, when 2-alkyl-4-methoxy-5-substituted aminophenol offormula (III) in which R⁴ is acetyl group or mesyl group is combinedwith a p-phenylenediamine derivative which is used as a color-developingmaterial, a bluish color tone of an extremely high chroma and a highfastness can be obtained. Furthermore, the color tone thus obtained ishighly resistant against light, washing and rubbing.

To further illustrate the present invention, and not by way oflimitation, the following Referential Examples and Examples will begiven.

EXAMPLE 1

(i) To 200 ml of acetone, were added 19.1 g (77.3 mmol) of2-methyl-4-hydroxy-5-nitrophenyl mesylate, 31.2 g of sodium carbonateand 19.2 g of dimethyl sulfate. The obtained mixture was heated underreflux for 3 hours. The reaction mixture was cooled and 700 ml of waterwas poured thereto. Then the mixture was extracted with 700 ml ofchloroform, and the extract was washed with water and dried overanhydrous Glauber's salt. After distilling off the solvent under reducedpressure, the residue was recrystallized from a solvent mixture(hexane/acetone (2:1, by volume)) to thereby give 15.4 g (59.1 mmol) of2-methyl-4-methoxy-5-nitrophenyl mesylate. The yield was 77%.

Physical properties of 2-methyl-4-methoxy-5-nitrophenyl mesylate:

m.p.: 110.0°-113.0° C.

¹ H-NMR spectra (200 MHz, CDCl₃): δppm; 2.44 (3H, s), 3.25 (3H, s), 3.97(3H, s), 6.98 (1H, s), 7.87 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 1524, 1372, 1346, 1172.

Elementary analysis data: calculated value for C₉ H₁₁ NO₆ S: C: 41.38%,H: 4.24%, N: 5.36%, S: 12.27%; analyzed value: C: 41.46%, H: 4.38%, N:5.36%, S: 12.28%.

(ii) In 110 ml of methanol was dissolved 15.5 g (59.4 mmol) of2-methyl-4-methoxy-5-nitrophenyl mesylate. Then 6.5 g of sodiumhydroxide dissolved in 20 ml of water was added thereto. The obtainedmixture was heated under reflux for 1 hour. After cooling, concentratedhydrochloric acid was added to thereby acidify the mixture. Then 400 mlof water was added and crystals were precipitated. The crystals werecollected by filtration and washed with water. Thus 10.9 g (59.4 mmol)of 2-methyl-4-methoxy-5-nitrophenol was obtained. The yield was 100%.

Physical properties of 2-methyl-4-methoxy-5-nitrophenol:

m.p.: 79.5°-80.5° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.21 (3H, s), 3.83 (3H, s),7.15 (1H, s), 7.29 (1H, s), 9.74 (1H, s).

IR spectra (KBR): νcm⁻¹ ; 3526, 1528, 1338.

Elementary analysis data: calculated value for C₈ H₉ NO₄ : C: 52.46%, H:4.95%, N: 7.65%; analyzed value: C: 52.55%, H: 5.06%, N: 7.55%.

(iii) 320 mg of 10% palladium-on-carbon, 2.90 g (15.8 mmol) of2-methyl-4-methoxy-5-nitrophenol and 75 ml of ethanol were fed into anautoclave (300 ml). The mixture was then hydrogenated at 50° C. under 50kg/cm² for 5 hours. After allowing to cool, the catalyst was filteredoff and the solvent was distilled off under reduced pressure. Thus 19.0g (12.4 mmol) of 2-methyl-4-methoxy-5-aminophenol was obtained in theform of brown crystals. The ¹ H-NMR spectra of this product showed noimpurities. The yield was 78%.

The 2-methyl-4-methoxy-5-aminophenol was purified by silica gel columnchromatography (Silica Gel 60, trade name, manufactured by Merck Co.,230-400 mesh, 200 g, eluent: acetone/chloroform (1:1, by volume)) anddissolved in ether. Then a hydrogen chloride gas was blown thereto tothereby give 2-methyl-4-methoxy-5-aminophenol hydrochloride.

Physical properties of 2-methyl-4-methoxy-5-aminophenol hydrochloride:

m.p.: 197°-203° C. (decomposed).

1H-NMR (200 MHz, DMSO-d₆): δppm: 2.12 (3H, s), 3.78 (3H, s), 6.96 (1H,s), 7.02 (1H, s), 9.05 (1H, br), 9.99 (3H, br).

IR spectra: νcm⁻¹ ; 3344, 2920.

Elementary analysis data: calculated value for C₈ H₁₂ NO₂ Cl: C: 50.67%,H: 6.38%, N: 7.39%, Cl: 18.69%; analyzed value: C: 50.68%, H: 6.33%, N:7.26%, Cl: 18.69%.

EXAMPLE 2

    ______________________________________                                        Base composition:    Content (%)                                              ______________________________________                                        oleic acid           10                                                       diethanolamide oleate                                                                               8                                                       oleyl alcohol         2                                                       polyoxyethylene octyldodecyl ether                                                                 10                                                       (average addition of EO: 20 mol)                                              ethanol              15                                                       propylene glycol     10                                                       ammonium chloride     3                                                       25% ammonia           7                                                       water                35                                                       ______________________________________                                    

To 100 g of a base consisting of the above composition were added 0.01mol of each color-developing material and 0.01 mol of each couplingagent, as specified in Tables 1 and 2 below. Next, the pH value of thecomposition was adjusted to 9.5 with ammonia. Thus the dyeingcomposition of the present invention and comparative dyeing compositionwere produced.

100 g of the dyeing composition of the present invention was mixed withthe same weight of a 6% aqueous solution of hydrogen peroxide to therebygive a dyeing solution. This dyeing solution was applied to humangrizzled hair and allowed to stand at 30° C. for 30 minutes. Then thehair was washed with the use of a common shampoo and dried. The colortone of hair thus dyed was observed. Table 1 shows the results. Thecolor tone, chroma, color intensity and dye stability for fading werealso evaluated. Table 2 shows the results. Each dyeing compositionshowed excellent dyeing properties.

The dye stability for fading was evaluated by comparing each sampleafter storing at 40° C. under 70% RH for 100 hours with a comparativesample stored at -5° C. with the naked eye.

COLOR-DEVELOPING MATERIAL

P₁ : p-aminophenol

P₂ : 5-aminosalicylic acid

P₃ : 2-chloro-4-aminophenol.

P₄ : 2,2,2-trifluoromethyl-4-aminophenol.

P₅ : p-phenylenediamine

P₆ : toluene-2,5-diamine

COUPLING AGENT

C₂ : 2-methyl-5-aminophenol

C₅ : 2-methyl-4-methoxy-5-aminophenol

C₆ : 2-methyl-4-methoxy-5-aminophenol hydrochloride.

CRITERIA FOR EVALUATION

A: very good.

B: average.

C: poor.

                  TABLE 1                                                         ______________________________________                                        Product of                                                                              Color-developing                                                                           Coupling                                               the invention                                                                           material     agent    Color tone                                    ______________________________________                                        1-1       P.sub.5      C.sub.5  reddish purple                                1-2       P.sub.6      C.sub.5  reddish purple                                1-3       P.sub.1      C.sub.5  red                                           1-4       P.sub.2      C.sub.5  orange red                                    1-5       P.sub.3      C.sub.5  orange yellow                                 1-6       P.sub.4      C.sub.5  yellow                                        1-7       P.sub.1      C.sub.6  red                                           ______________________________________                                    

                  TABLE 2                                                         ______________________________________                                                 Product of     Comparative                                                    the Invention  Product                                                        1-3   1-4      1-7     1-1   1-2                                     ______________________________________                                        Color-developing                                                                         P.sub.1 P.sub.2  P.sub.1                                                                             P.sub.1                                                                             P.sub.2                               material                                                                      Coupling agent                                                                           C.sub.5 C.sub.5  C.sub.6                                                                             C.sub.2                                                                             C.sub.2                               Dyed hair trace:                                                              Color tone red     orange   red   red   orange                                                   red                  red                                   Chroma     A       A        A     B     B                                     Color intensity                                                                          A       A        A     B     B                                     Dye stability for                                                                        A       A        A     B     B                                     fading                                                                        ______________________________________                                    

EXAMPLE 3

(i) To 13 ml of acetic anhydride were added 1.90 g (12.1 mmol) of2-methyl-4-methoxy-5-aminophenol and 0.1 ml of concentrated sulfuricacid. The mixture was stirred at room temperature for 2 hours. Afterallowing to cool, 50 ml of (ice-)cold water was poured thereto and themixture was allowed to stand overnight to thereby decompose the aceticanhydride. The crystals thus precipitated were filtered andrecrystallized from benzene. Thus 1.85 g (7.8 mmol) of2-methyl-4-methoxy-5-acetylaminophenyl acetate was obtained. The yieldwas 65%.

Physical properties of 2-methyl-4-methoxy-5-acetylaminophenyl acetate:

m.p.: 150.5°-151.3° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.06 (3H, s), 2.07 (3H, s),2.27 (3H, s), 3.82 (3H, s), 6.92 (1H, s), 7.70 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3322, 2962, 2842, 1755, 1662.

Elementary analysis data: calculated value for C₁₂ H₁₅ NO₄ : C: 60.96%,H: 6.39%, N: 5.92%; analyzed value: C: 60.89%, H: 6.60%, N: 5.84%.

(ii) To 35 ml of a 0.4N aqueous solution of sodium hydroxide were added1.70 g (7.17 mmol) of 2-methyl-4-methoxy-5-acetylaminophenyl acetate and10 ml of ethanol. The mixture was stirred at room temperature for 10minutes. When crystals were completely dissolved, the stirring wasceased. Then 0.3 ml of acetic acid was added and thus crystals wereprecipitated. The crystals were collected by filtration, purified bycolumn chromatography (Silica Gel 60, trade name, manufactured by MerckCo., 230-400 mesh, 200 g, eluent: ethyl acetate) and recrystallized fromthe solvent mixture of ethyl acetate/hexane (2:1). Thus 1.05 g (5.38mmol) of 2-methyl-4-methoxy-5-acetylaminophenol was obtained. The yieldwas 75%.

Physical properties of 2-methyl-4-methoxy-5-acetylaminophenol

m.p.: 212.0°-215.4° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.17 (3H, s), 2.19 (3H, s),3.84 (3H, s), 6.85 (1H, s), 7.67 (1H, s), 8.94 (1H, s), 9.04 (1H, brs).

IR spectra (KBr): νcm⁻¹ ; 3390, 3136, 1653.

Elementary analysis data: calculated value for C₁₀ H₁₃ NO₃ : C: 61.53%,H: 6.71%, N: 7.17%; analyzed value: C: 6.54%, H: 7.06%, N: 7.10%.

EXAMPLE 4

(i) 20 ml of pyridine was cooled to 0° C. and 2.10 g (3.70 mmol) of2-methyl-4-methoxy-5-aminophenol and 5.3 g of methanesulfonyl chloridewere added thereto. The mixture was adjusted to room temperaturefollowed by stirring for 1 hour. Then 200 ml of water was poured theretoand the mixture was extracted with 300 ml of chloroform, and the extrawas washed with 2N hydrochloric acid and a saturated aqueous solution ofsodium hydrogencarbonate and dried over anhydrous Glauber's salt. Afterdistilling off the solvent under reduced pressure, brown crystals wereobtained. These crystals were purified by column chromatography (thesame as the one used in Example 3) and recrystallized from the solventmixture of ethyl acetate/hexane (2:1). Thus 2.01 g (6.50 mmol) of2-methyl-4-methoxy-5-mesylaminophenyl mesylate was obtained. The yieldwas 47%.

Physical properties of 2-methyl-4-methoxy-5-mesyl-aminophenyl mesylate:

m.p.: 114.5°-115.5° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆); δppm; 2.27 (3H, s), 2.94 (3H, s),3.40 (3H, s), 3.89 (3H, s), 7.06 (1H, s), 7.22 (1H, s), 9.10 (1H, brs).

IR spectra (KBr): νcm⁻¹ ; 3248, 1354, 1332, 1174, 1154.

Elementary analysis data: calculated value for C₁₀ H₁₅ NO₆ S: C: 38.83%,H: 4.89%, N: 4.53%, S: 20.73%; analyzed value: C: 38.77%, H: 5.24%, N:4.50%, S: 20.77%.

(ii) To 50 ml of water were added 3.0 g of sodium hydroxide and 1.40 g(4.53 mmol) of 2-methyl-4-methoxy-5-mesylphenyl mesylate. The mixturewas heated under reflux for 1 hour. After cooling, 10 ml of concentratedhydrochloric acid was added thereto and thus crystals were precipitated.These crystals were collected by filtration, washed with water andrecrystallized from the solvent mixture of ethyl acetate/hexane (2:1).Thus 0.72 g (3.12 mmol) of 2-methyl-4-methoxy-5-mesylaminophenol wasobtained. The yield was 69%.

Physical properties of 2-methyl-4-methoxy-5-mesylaminophenol:

m.p.: 153.1°-154.3° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆); δppm; 2.09 (3H, s), 2.87 (3H, s),3.72 (3H, s), 6.76 (1H, s), 6.80 (1H, s), 8.67 (1H, brs), 8.96 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3442, 3256, 1308, 1203, 1155.

Elementary analysis data: calculated value for C₉ H₁₃ NO₄ S: C: 46.74%,H: 5.67%, N: 6.06%, S: 13.86%; analyzed value: C: 46.82%, H: 6.06%, N:6.04%, S: 13.88%.

EXAMPLE 5

    ______________________________________                                        Base composition:    Content (%)                                              ______________________________________                                        oleic acid           10                                                       diethanolamide oleate                                                                               8                                                       oleyl alcohol         2                                                       polyoxyethylene octyldodecyl ether                                                                 10                                                       (average addition of EO: 20 mol)                                              ethanol              15                                                       propylene glycol     10                                                       ammonium chloride     3                                                       25% ammonia           7                                                       water                35                                                       ______________________________________                                    

To 100 g of a base consisting of the above composition, were added 0.01mol of each color-developing material and 0.01 mol of each couplingagent, as specified in Table 3 or 4 below. Next, the pH value of thecomposition was adjusted to 9.5 with ammonia. Thus the dyeingcomposition of the present invention and the comparative dyeingcomposition were produced.

100 g of the dyeing composition of the present invention was mixed withthe same weight of a 6% aqueous solution of hydrogen peroxide to therebygive a dyeing solution. This dyeing solution was applied to humangrizzled hair and allowed to stand at 30° C. for 30 minutes. Then thehair was washed with the use of a common shampoo and dried. The colortone of hair thus dyed was observed. Table 3 shows the results. Thecolor tone, chroma and dye stability for fading of the dye were alsoevaluated. Table 4 shows the results. Each dyeing composition showedexcellent dyeing properties.

The dye stability for fading was evaluated by comparing each sampleafter storing at 40° C. under RH 70% for 100 hours with a comparativesample stored at -5° C. with the naked eye.

COLOR-DEVELOPING MATERIAL

P₁ : p-aminophenol

P₂ : 5-aminosalicylic acid.

P₅ : p-phenylenediamine

P₆ : toluene-2,5-diamine

COUPLING AGENT

C₇ : 2-methyl-4-methoxy-5-acetylaminophenol

C₈ : m-phenylenediamine.

CRITERIA FOR EVALUATION

A: very good.

B: good.

C: somewhat poor.

D: poor.

                  TABLE 3                                                         ______________________________________                                        Product of                                                                              Color-developing                                                                           Coupling                                               the invention                                                                           Material     agent    Color-tone                                    ______________________________________                                        2-1       P.sub.5      C.sub.7  blue                                          2-2       P.sub.6      C.sub.7  violet blue                                   2-3       P.sub.1      C.sub.7  Orange yellow                                 2-4       P.sub.2      C.sub.7  Yellow                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                                 Product of       Comparative                                                  the Invention    product                                                      2-1  2-2     2-3     2-4   2-1  2-2                                  ______________________________________                                        Color-developing                                                                         P.sub.5                                                                              P.sub.6 P.sub.1                                                                             P.sub.2                                                                             P.sub.5                                                                            P.sub.6                            material                                                                      Coupling agent                                                                           C.sub.7                                                                              C.sub.7 C.sub.7                                                                             C.sub.7                                                                             C.sub.8                                                                            C.sub.8                            Dyed hair trace:                                                              Color tone blue   violet  orange                                                                              yellow                                                                              blue blue                                                 blue    yellow                                              Chroma     A      A       B     B     B    B                                  Dye stability                                                                            A      A       A     A     D    D                                  for fading                                                                    ______________________________________                                    

EXAMPLE 6

(i) To 20 ml of dioxane were added 5.10 g (33.3 mmol) of2-methyl-4-methoxy-5-aminophenol and 1.86 g of calcium carbonate, andthe temperature of the mixture was evaluated to 90° C. 3.90 ml (5.38mmol) of β-chloroethyl chloroformate was added thereto and the resultingmixture was stirred at 90° C. for 1 hour. After cooled with ice,insoluble inorganic salts were filtered off and 150 ml of (ice-)coldwater was poured into the filtrate. The crystals thus precipitated werefiltered and washed with water. Thus, 5.80 g (22.3 mmol) ofN-(2-methoxy-4-methyl-5-hydroxyphenyl)-β-chloroethyl carbamate wasobtained. The yield was 67%.

Physical properties ofN-(2-methoxy-4-methyl-5-hydroxyphenyl)-β-chloroethyl carbamate:

m.p.: 177.0°-180.5° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.07 (3H, s), 3.69 (3H, s),3.83 (2H, t, J=5.3 Hz), 4.30 (2H, t, J=5.3 Hz), 6.73 (1H, s), 7.16 (1H,s), 8.32 (1H, s), 8.85 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3408, 1694.

Elementary analysis data: caluculated value for C₁₁ H₁₄ NO₄ Cl: C:50.88%, H: 5.43%, N: 5.39%, Cl: 13.65%; analyzed value: C: 50.70%, H:5.41%, N: 5.11%, Cl: 13.59%.

(ii) To 10 ml of water was added 1.87 g of sodium hydroxide, and thetemperature of the solution was elevated to 45° C. 5.50 g (21.2 mmol) ofN-(2-methoxy-4-methyl-5-hydroxyphenyl)-2-chloroethyl carbamate was addedthereto and the resulting mixture was stirred at 45° C. for 15 minutes.After cooled with ice, 20 ml of (ice)-cold water was poured into thereaction mixture and concentrated hydrochloric acid was added theretountil no further crystals were precipitated. The crystals were collectedby filtration, washed with water and recrystallized from ethanol. Thus3.03 g (13.6 mmol) ofN-(2-methoxy-4-methyl-5-hydroxyphenyl)-1,3-oxazolidin-2-one wasobtained. The yield was 64%.

Physical properties ofN-(2-methoxy-4-methyl-5-hydroxyphenyl)-1,3-oxazolidin-2-one:

m.p.: 193.5°-196.8° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.13 (3H, s), 3.71 (3H, s),3.82 (2H, t, J=7.5 Hz), 4.39 (2H, t, J=7.5 Hz), 6.71 (1H, s), 6.84 (1H,s), 9.03 (1H, s).

IR spectra: νcm⁻¹ ; 3256, 1714.

Elementary analysis data: caluculated value for C₁₁ H₁₃ NO₄ : C: 59.19%,H: 5.87%, N: 6.27%; analyzed value: C: 59.28%, H: 5.94%, N: 6.22%.

(iii) 10 ml of 5N sodium hydroxide was heated to 70° C., and 2.76 g(12.4 mmol) ofN-(2-methoxy-4-methyl-5-hydroxyphenyl)-1,3-oxazolidin-2-one was addedthereto, and then the resulting mixture was stirred at 70° C. for 1hour. After allowing to cool, 40 ml of water was poured into thereaction mixture, and acetic acid was added thereto until no furthercrystals were precipitated. The crystals were filtered, washed withwater and recrystallized from the solvent mixture of water/ethanol (4:1,by volume). Thus, 1.10 g (5.6 mmol) of2-methyl-4-methoxy-5-(β-hydroxyethylamino)phenol was obtained. The yieldwas 45%.

Physical properties of 2-methyl-4-methoxy-5-(β-hydroxyethylamino)phenol:

m.p.: 81.5°-82.5° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 1.99 (3H, s), 2.99 (2H, t, d,J=5.5, 5.5 Hz), 3.57 (2H, t, d, J=5.5, 5.5 Hz), 3.66 (3H, s), 4.51 (1H,brt, J=5.5 Hz), 4.78 (1H, t, J=5.5 Hz), 6.07 (1H, s), 6.52 (1H, s), 8.41(1H, s).

IR-spectra (KBr): νcm⁻¹ ; 3440, 3345, 3240.

Elementary analysis data: caluculated value for C₁₀ H₁₆ NO₃ Cl: C:51.40%, H: 6.90%, N: 5.99%, Cl: 15.17%; analyzed value: C: 51.39%, H:6.88%, N: 5.91%, Cl: 15.03%.

EXAMPLE 7

    ______________________________________                                        Base composition:    Content(%)                                               ______________________________________                                        oleic acid           10                                                       diethanolamide oleate                                                                               8                                                       oleyl alcohol         2                                                       polyoxyethylene octyldodecyl ether                                                                 10                                                       (average addition of EO: 20 mol)                                              ethanol              15                                                       propylene glycol     10                                                       ammonium chloride     3                                                       25% ammonia           7                                                       water                35                                                       ______________________________________                                    

To 100 g of a base consisting of the above composition were added 0.01mol of each color-developing material and 0.01 mol of each couplingagent, as specified in Tables 5 and 6 below. Next, the pH value of thecomposition was adjusted to 9.5 with ammonia. Thus the dyeingcompositions of the present invention and comparative dyeingcompositions were produced.

100 g of the dyeing composition of the present invention was mixed withthe same weight of a 6% aqueous solution of hydrogen peroxide to therebygive a dyeing solution. This dyeing solution was applied to humangrizzled hair and allowed to stand at 30° C. for 30 minutes. Then thehair was washed with the use of a common shampoo and dried. The colortone of hair thus dyed was observed. Table 5 shows the results. Thecolor tone, chroma, color intensity and dye stability for fading of thedye were also evaluated. Table 6 shows the results. Each dyeingcomposition showed excellent dyeing properties.

The dye stability for fading was evaluated by comparing each sampleafter storing at 40° C. under 70% RH for 100 hours with a comparativesample stored at -5° C. with the naked eye.

COLOR-DEVELOPING MATERIAL

P₁ : p-aminophenol

P₂ : 5-aminosalicylic acid

P₃ : 2-chloro-4-aminophenol.

P₄ : 2,2,2-trifluoromethyl-4-aminophenol.

P₅ : p-phenylenediamine

P₆ : toluene-2,5-diamine

COUPLING AGENT

C₁ : 2-methyl-4-methoxy-5-(2-hydroxyethyl)aminophenol

C₂ : 2-methyl-5-aminophenol

C₃ : 2-methyl-5-(2-hydroxyethyl)aminophenol

C₄ : 2-methyl-4-methoxy-5-(2-hydroxyethyl)aminophenol hydrochloride.

CRITERIA FOR EVALUATION

A: very good.

B: average.

C: poor.

                  TABLE 5                                                         ______________________________________                                        Product of                                                                              Color-developing                                                                           Coupling                                               the invention                                                                           material     agent    Color tone                                    ______________________________________                                        3-1       P.sub.1      C.sub.1  red                                           3-2       P.sub.2      C.sub.1  orange red                                    3-3       P.sub.3      C.sub.1  orange red                                    3-4       P.sub.4      C.sub.1  yellow                                        3-5       P.sub.5      C.sub.1  reddish purple                                3-6       P.sub.6      C.sub.1  reddish purple                                ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                               Product of  Comparative                                                       the Invention                                                                             product                                                           3-1  3-2     3-3    3-1  3-2   3-3  3-4                                ______________________________________                                        Color-   P.sub.1                                                                              P.sub.2 P.sub.1                                                                            P.sub.1                                                                            P.sub.2                                                                             P.sub.1                                                                            P.sub.2                          developing                                                                    material                                                                      Coupling C.sub.1                                                                              C.sub.1 C.sub.4                                                                            C.sub.2                                                                            C.sub.2                                                                             C.sub.3                                                                            C.sub.3                          agent                                                                         Dyed hair                                                                     trace:                                                                        Color tone                                                                             red    orange  red  red  orange                                                                              red  orange                                           red               red        red                              Chroma   A      A       A    B    B     B    B                                Color    A      A       A    B    B     B    B                                intensity                                                                     Dye stability                                                                          A      A       A    B    B     A    A                                for fading                                                                    ______________________________________                                    

EXAMPLE 8

(i) 1.55 g of 10% palladium-on-carbon, 18.8 g (71.9 mmol) of2-methyl-4-methoxy-5-nitrophenyl mesylate and 120 ml of ethanol were fedinto an autoclave (200 ml), and the mixture was then hydrogenated at 50°C. under 50 g/cm² for 1 hours with stirring. After allowing to cool,palladium-on-carbon was filtered off and the solvent was distilled offunder reduced pressure to obtain brown crystals. The crystals thusobtained were recrystallized from ethanol to thereby give 13.4 g (58.2mmol) of 2-methyl-4-methoxy-5-aminophenyl mesylate in the form of yellowneedle-like crystals. The yield was 81%.

Physical properties of 2-methyl-4-methoxy-5-aminophenyl mesylate:

m.p.: 87.0°-88.0° C.

¹ H-NMR spectra (200 MHz, CDCl₃): δppm; 2.24 (3H, s), 3.13 (3H, s), 3.83(3H, s), 6.79 (1H, s), 6.85 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3464, 3380, 1518, 1352.

Elementary analysis data: calculated value for C₉ H₁₃ NO₄ S: C: 46.74%,H: 5.67%, N: 6.06%, S: 13.86%. analyzed value: C: 46.74%, H: 5.67%, N:5.85%, S: 13.80%.

(ii) 7.52 g (32.6 mmol) of 2-methyl-4-methoxy-5-aminophenyl mesylate, 90ml of ethanol and 4.2 ml (3.5 g, 60 mmol) of propylene oxide were fedinto an autoclave (200 ml) and the mixture was stirred at 70° C. for 35hours. After allowing to cool, the solvent was distilled off underreduced pressure to obtain a brown oily matter. The oily matter thusobtained was subjected to silica gel chromatography (Silica Gel 60,trade name, manufactured by Merck Co., 70-230 mesh, 300 g, eluent:chloroform/ethyl acetate (1:1 by volume)), and thereby give 0.33 g (1.4mmol, 6%) of the starting material from the first fraction, 6.46 g (22.4mmol, 69%) of 2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenyl mesylatefrom the second fraction in the form of an oily matter and 1.81 g (5.2mmol, 16%) of 2-methyl-4-methoxy-5-bis(2-hydroxypropyl)aminophenylmesylate from the third fraction in the form of brown crystals.

Physical properties of 2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenylmesylate:

Form: pale yellow oil.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 1.11 (3H, d, J=6.8 Hz), 2.15(3H, s), 2.83 (1H, m), 3.01 (1H, m), 3.34 (3H, s), 3.79 (3H, s), 3.82(1H, m), 4.5 (br), 6.45 (1H, s), 6.73 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3450, 1532, 1362.

Elementary analysis data: calculated value for C₁₂ H₁₉ NO₅ S: C: 49.81%,H: 6.62%, N: 4.84%, S: 11.08%; analyzed value: C: 49.52%, H: 6.85%, N:5.02%, S: 10.88%.

Physical properties of2-methyl-4-methoxy-5-bis(2-hydroxypropyl)aminophenyl mesylate:

m.p.: 128.0°-129.0° C.

¹ H-NMR spectra (200 MHz, CDCl₃): δppm; 1.09 (6H, s, J=6.2 Hz), 2.34(3H, s), 2.8 (2H, m), 3.1 (2H, s), 3.17 (3H, s), 3.50 (2H, br), 3.61(2H, m), 3.88 (3H, s), 6.78 (1H, s), 7.16 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3272, 1514, 1364.

Elementary analysis data: calculated value for C₁₅ H₂₅ NO₆ S: C: 51.86%,H: 7.25%, N: 4.03%, S: 9.23%. analyzed value: C: 51.78%, H: 7.21%, N:3.78%, S: 9.35%.

(iii) Into 100 ml of methanol was added 2.0 g (13.1 mmol) of2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenyl mesylate. Afterconducting nitrogen substitution at room temperature, 40 ml of 7.5Naqueous solution of sodium hydroxide was added to the mixture and theresulting mixture was heated under reflux for 7 hours with blowingnitrogen gas thereinto. After allowing to cool, the mixture wasneutralized with acetic acid and poured into 400 ml of water. Theresulting solution was extracted with 400 ml of ethyl acetate. Theorganic layer was washed with a saturated aqueous solution of commonsalt and dried over anhydrous sodium sulfate. The solvent was distilledoff under reduced pressure to obtain an oily matter. The oily matter wascrystallized from the solvent mixture of hexane/ethyl acetate (1:1 byvolume) to give 2.30 g (10.9 mmol) of2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenol. The yield was 49%.

Physical properties of2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenol:

m.p.: 124.5°-126.0° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 1.26 (3H, d,J=6.7 Hz), 2.17(3H, d,J=6.7 Hz), 2.99 (1H, dd,J=13.4, 7.3 Hz), 3.18 (1H, dd,J=13.4, 4.6Hz), 3.80 (3H, s), 4.04 (1H, m), 4.5 (br), 6.21 (1H, s), 6.54 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3420, 3384, 3340 (sh.)

Elementary analysis data: calculated value for C₁₁ H₁₇ NO₃ : C: 62.54%,H: 8.11%, N: 6.63%; analyzed value: C: 62.45%, H: 8.11%, N: 6.56%.

EXAMPLE 9

Into 15 ml of benzene were added 2.10 g (13.7 mmol) of2-methyl-4-methoxy-5-aminophenol, 1.28 g (13.9 mmol, 1.0 eq.) of methylfluoroacetate and 1.64 g (30.4 mmol) of sodium methoxide and the mixturewas heated under reflux for 6.5 hours. After allowing to cool, themixture was poured into 300 ml of water, and neutralized with aceticacid and extracted with 200 ml of ethyl acetate. The organic layer waswashed with a saturated aqueous solution of common salt and dried overanhydrous sodium sulfate. The solvent was distilled off under reducedpressure to obtain dark-brown crystals. The crystals were purified bysilica gel column chromatography (Silica Gel 60, trade name,manufactured by Merck Co., 70-230 mesh, 200 g, eluent: ethyl acetate)and pale brown solid matters were obtained from the 600-900 ml fraction.The solid matters were recrystallized from the solvent mixture ofhexane/ethyl acetate (2:1 by volume) to give 230 mg (1.9 mmol) of2-methyl-4-methoxy-5-fluoroacetylaminophenol. The yield was 8%.

Physical properties of 2-methyl-4-methoxy-5-fluoroacetylaminophenol:

m.p.: 171.5°-173.0° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.08 (3H, 2), 3.75 (3H, s),4.99 (2H, d, J=46.7 Hz), 6.80 (1H, s), 7.60 (1H, s), 8.88 (1H, brs),8.95 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3428, 3224, 1676.

Elementary analysis data: calculated value for C₁₀ H₁₂ NO₃ F: C: 56.33%,H: 5.67%, N: 6.57%; analyzed value: C: 56.08%, H: 5.88%, N: 6.50%.

EXAMPLE 10

2.08 g (11.0 mmol) of 2-methyl-4-methoxy-5-aminophenol was added to 200ml of pyridine and the mixture was cooled to 0° C. 4.20 g (24.1 mmol,2.2 eq.) of difluoroacetic anhydride was added to the mixture and themixture was stirred at room temperature for 30 minutes. The mixture waspoured into 200 ml of water and the mixture was extracted with 200 ml ofchloroform. The organic layer was washed with a saturated aqueoussolution of common salt and dried over anhydrous sodium sulfate. Thesolvent was distilled off under reduced pressure to obtain crystals. Thecrystals were added to 35 ml of 0.4N aqueous solution of sodiumhydroxide and 10 ml of ethanol was added thereto, followed by stirringat room temperature for 15 minutes. The solution was neutralized withacetic acid and the crystals thus precipitated were filtered out. Thecrystals were recrystallized from the solvent mixture of hexane/ethylacetate (2:1 by volume) to give 1.30 g (5.6 mmol) of2-methyl-4-methoxy-5-difluoroacetylaminophenol in the form of colorlesscrystals. The yield was 52%.

Physical properties of 2-methyl-4-methoxy-5-difluoroacetylaminophenol:

m.p.: 202.0°-204.0° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δppm; 2.10 (3H, s), 3.75 (3H, s),6.46 (1H, t, J=52.9 Hz), 6.82 (1H, s), 7.44 (1H, s), 9.00 (1H, s), 9.75(1H, brs).

IR spectra (KBr): νcm⁻¹ ; 3408, 3304, 1694.

Elementary analysis data: calculated value for C₁₀ H₁₁ NO₃ F₂ : C:51.95%, H: 4.80%, N: 6.06%, analyzed value: C: 52.11%, H: 4.85%, N:6.08%.

EXAMPLE 11

2.0 g (13.1 mmol) of 2-methyl-4-methoxy-5-aminophenol was added to 20 mlof pyridine and the mixture was cooled to 0° C. 3.0 ml (4.5 g, 21 mmol)of trifluoroacetic anhydride was added to the mixture and stirred atroom temperature for 2 hours. The mixture was poured into 200 ml ofwater and the mixture was extracted with 300 ml of chloroform. Theorganic layer was washed with a saturated aqueous solution of commonsalt and dried over anhydrous sodium sulfate. The solvent was distilledoff under reduced pressure to obtain dark-brown solid matter. The solidmatter was purified by silica gel column chromatography (Silica Gel 60,trade name, manufactured by Merck Co., 70-230 mesh, 100 g, eluent: ethylacetate) and thereby colorless crystals were obtained from the 200-500ml fraction. The crystals were recrystallized from the solvent mixtureof hexane/ethyl acetate (2:1 by volume) to give 280 mg (1.1 mol) of2-methyl-4-methoxy-5-trifluoroacetylaminophenol in the form of colorlesscrystals. The yield was 9%.

Physical properties of 2-methyl-4-methoxy-5-trifluoroacetylaminophenol:

m.p.: 201.5°-203.0° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆): δ ppm: 2.12 (3H, s), 3.74 (3H, s),6.89 (1H, s), 6.92 (1H, s), 9.08 (1H, s), 10.45 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3400, 1713.

Elementary analysis data: calculated value for C₁₀ H₁₀ NO₃ F₃ : C:48.26%, H: 4.04%, N: 5.62%; analyzed value: C: 48.50%, H: 4.19%, N:5.57%.

EXAMPLE 12

(i) 2 g (10.6 mmol) of 2-methyl-4-methoxy-5-aminophenol and 4.9 g (21.7mmol) of benzoic anhydride were dissolved into 200 ml of pyridine andthe solution was stirred at room temperature overnight. The solution waspoured over ice, and solid matters thus precipitated were collected byfiltration followed by washed with water and recrystallized from thesolvent mixture of benzene/hexane to give 3.10 g (8.6 mmol) of2-methyl-4-methoxy-5-benzoylaminophenyl benzoate in the form of palebrown crystals. The yield was 81%.

Physical properties of 2-methyl-4-methoxy-5-benzoylaminophenyl benzoate:

m.p.: 203.5°-207.8° C.

¹ H-NMR spectra (200 MHz, CDCl₃); δ ppm; 8.53 (broad s, 1H, NHB₂), 8.41(s, 1H, arm-H), 8.37 (dd, J₁ =1.3 Hz, J₂ =8.3 Hz, 2H, arm-H), 8.03 (dd,J₁ =1.8 Hz, J₂ =7.6 Hz, 2H, arm-H), 7.4-7.7 (m, 6H, arm-H), 6.81 (s, 1H,arm-H), 3.95 (s, 3H, CH₃ O), 2.22 (s, 2H, CH₃).

IR spectra (KBr): νcm⁻¹ ; 1654, 1722.

Elementary analysis data: caluculated value for C₂₂ H₁₉ NO₄ : C: 73.12%,H: 5.30%, N: 3.88%; analuzed value: C: 73.00%, H: 5.52%, N: 4.16%.

(ii) 3 g (8.3 mmol) of 2-methyl-4-methoxy-5-benzoylaminophenyl benzoatewas added into the mixture of 50 ml of sodium hydroxide and 50 ml ofethanol and the solution was heated at 100° C. under reflux for 2.5hours. 40 ml of IN hydrochloric acid was added to the reaction mixtureand precipitates were filtered, washed with water and recrystallizedfrom ethanol to give 1.2 g (4.6 mmol) of2-methyl-4-methoxy-5-benzoylaminophenol in the form of pale yellowplate-like crystals. The yield was 78%.

Physical properties of 2-methyl-4-methoxy-5-benzoylaminophenol:

m.p.: 193.1°-193.4° C.

¹ H-NMR spectra (200 MHz, CDCl₃); δ ppm; 8.60 (broad s, 1H, NHB₂), 8.42(s, 1H, arm-H), 7.92-7.88 (m, 2H, arm-H), 7.46-7.64 (broad d, 4H, arm-H,OH), 6.70 (s, 1H, arm-H), 3.88 (s, 3H, CH₃ O), 2.25 (s, 3H, CH₃).

IR spectra (KBr): νcm⁻¹ ; 3244, 1644.

Elementary analysis data: caluculated value for C₁₅ H₁₅ NO₃ : C: 70.02%,H: 5.88%, N: 5.44%; analyzed value: C: 70.17%, H: 6.03%, N: 5.44%.

EXAMPLE 13

5.0 g (32.7 mmol) of 2-methyl-4-methoxy-5-aminophenol, 500 ml ofpalladium-on-carbon, 100 ml of methanol and 1.72 g of acetaldehyde werefed into an autoclave (200 ml). The mixture was then hydrogenated at 50°C. under 50 kg/cm² for 6 hours. After allowing to cool, thepalladium-on-carbon was filtered off and the solvent was distilled offunder reduced pressure to obtain brown crystals. The crystals wereseparated and purified by silica gel column chromatography (Silica Gel60, trade name, manufactured by Merck Co., 230-400 mesh, 300 g, eluent:ethyl acetate/hexane (1:1 by volume) to give 2.62 g (14.5 mmol) of2-methyl-4-methoxy-5-ethylaminophenol from the first fraction in theform of pale red crystals and 1.86 g (8.90 mmol) of2-methyl-4-methoxy-5-diethylaminophenol from the second fraction in theform of pale yellow crystals. The yields were 44% and 27%, respectively.Each of 2-methyl-4-methoxy-5-ethylaminophenol and2-methyl-4-methoxy-5-diethylaminophenol was purified byrecrystallization from the solvent mixture of ethyl acetate/hexane (1:2by volume).

Physical properties of 2-methyl-4-methoxy-5-ethylaminophenol:

m.p.: 110.2°-110.9° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆); δ ppm; 1.14 (3H, t, J=7.2 Hz), 1.98(1H, s), 2.47 (2H, dq, J=7.2, 7.2 Hz), 3.65 (3H, s), 4.34 (1H, brt,J=7.2 Hz), 6.05 (1H, s), 6.48 (1H, s), 8.38 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3324, 3132, 1204.

Elementary analysis data: calculated value for C₁₀ H₁₅ NO₂ : C: 66.27%,H: 8.34%, N: 7.73%; analyzed value: C: 66.48%, H: 8.39%, N: 7.71%.

Physical properties of 2-methyl-4-methoxy-5-diethylaminophenol:

m.p.: 94.0°-95.0° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆); δ ppm; 0.92 (6H, t, J=7.2 Hz), 2.04(3H, s), 3.00 (4H, q, J=7.2 Hz), 3.66 (3H, s), 6.38 (1H, s), 6.60 (1H,s), 8.52 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3180, 2976, 1208.

Elementary analysis data: calculated value for C₁₂ H₁₉ NO₂ : C: 68.87%,H: 9.15%, N: 6.69%; analyzed value: C: 68.90%, H: 9.11%, N: 6.61%.

EXAMPLE 14

5.0 g (32.7 mmol) of 2-methyl-4-methoxy-5-aminophenol, 500 ml ofpalladium-on-carbon, 100 ml of methanol and 3.36 g of 35% formalin werefed into an autoclave (200 ml). The mixture was then hydrogenated at 50°C. under 50 kg/cm² for 6 hours. After allowing to cool, thepalladium-on-carbon was filtered off and the solvent was distilled offto obtain brown crystals. The crystals were separated and purified bysilica gel column chromatography (Silica Gel 60, trade name,manufactured by Merck Co., 230-400 mesh, eluent: ethyl acetate/hexane(1:1 by volume)) to thereby give 2.45 g (14.7 mmol) of2-methyl-4-methoxy-5-methylaminophenol from the first fraction in theform of pale brown crystals and 1.82 g (10.1 mmol) of2-methyl-4-methoxy-5-dimethylaminophenol from the second fraction in theform of brown crystals. The yields were 45% and 31%, respectively. Then,2-methyl-4-methoxy-5-methylaminophenol was dissolved into 50 ml ofethanol and a hydrogen chloride gas was blown thereto followed byaddition of acetonitrile to thereby give2-methyl-4-methoxy-5-methyl-aminophenol hydrochloride as the purifiedcrystals. While 2-methyl-4-methoxy-5-dimethylaminophenol wasrecrystallized from the solvent mixture of ethyl acetate/hexane (1:2 byvolume).

Physical properties of 2-methyl-4-methoxy-5-methylaminophenolhydrochloride:

m.p.: 230.5°-233.0° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆); δ ppm; 2.13 (3H, s), 2.76 (3H, s),3.79 (3H, s), 6.96 (1H, s), 7.01 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3620, 3210, 2660, 2452, 1208.

Elementary analysis data: calculated value for C₉ H₁₄ NO₂ Cl: C: 53.08%,H: 6.93%, N: 6.88%, Cl: 17.41%; analyzed value: C: 52.84%, H: 6.98%, N:7.05%, Cl: 17.27%.

Physical properties of 2-methyl-4-methoxy-5-dimethylaminophenol:

m.p.: 109.5°-110.5° C.

¹ H-NMR spectra (200 MHz, DMSO-d₆); δ ppm; 2.04 (3H, s), 2.60 (6H, s),3.66 (3H, s), 6.34 (1H, s), 6.58 (1H, s), 8.55 (1H, s).

IR spectra (KBr): νcm⁻¹ ; 3150, 2960, 1202.

Elementary analysis data: calculated value for C₁₀ H₁₅ NO₂ : C: 66.27%,H: 8.34%, N: 7.73%. analyzed value: C: 66.42%, H: 8.25%, N: 7.85%.

EXAMPLE 15

The dyeing compositions of the present invention and the comparativedyeing compositions were produced in accordance with the manner as inExample 2 except that the color-developing material and the couplingagent each specified in table 7 or 8 below were used.

The dyeing solution was produced in the manner as in Example 2. Thisdyeing solution was applied to human grizzled hair and allowed to standat 30° C. for 30 minutes. Then the hair was washed with the used of acommon shampoo and dried. The color tone of the hair thus dyed wasobserved. Table 7 shows the results. The color tone, chroma, colorintensity, and dye stability for fading were also evaluated. Table 8shows the results. Each dyeing composition showed excellent dyeingproperties.

The dye stability for fading was evaluated by comparing each sampleafter storing at 40° C. under 70% RH for 100 hours with ac comparativesample stored at -5° C. with the naked eye.

COLOR-DEVELOPING MATERIAL

P₁ : p-aminophenol

P₂ : 5-aminosalicyclic acid

P₃ : 2-chloro-4-aminophenol

P₄ : 2,2,2-trifluoromethyl-4-aminophenol

P₅ : p-phenylenediamine

P₆ : toluene-2, 5-diamine

COUPLING AGENT

C₉ : 2-methyl-4-methoxy-5-methylaminophenol

C₁₀ : 2-methyl-4-methoxy-5-dimethylaminophenol

C₁₁ : 2-methyl-4-methoxy-5-ethylaminophenol

C₁₂ : 2-methyl-4-methoxy-5-diethylaminophenol

C₁₃ : 2-methyl-4-methoxy-5-(2-hydroxypropyl)aminophenol

C₁₇ : 2-methyl-4-methoxy-5-mesylaminophenol

C₁₈ : 2-methyl-4-methoxy-5-benzoylaminophenol

C₁₉ : 2-methyl-4-methoxy-5-fluoroacetylaminophenol

C₂₀ : 2-methyl-4-methoxy-5-difluoroacetylaminophenol

C₂₁ : 2-methyl-4-methoxy-5-trifluoroacetylaminophenol

CRITERIA FOR EVALUATION

A: Very good.

B: average.

C: poor.

                  TABLE 7                                                         ______________________________________                                        Product of                                                                              Color-developing                                                                           Coupling                                               the invention                                                                           material     agent    Color tone                                    ______________________________________                                        4-1       P.sub.1      C.sub.9  red                                           4-2       P.sub.5      C.sub.9  Reddish purple                                4-3       P.sub.6      C.sub.9  reddish purple                                4-4       P.sub.1      C.sub.10 Pink                                          4-5       P.sub.5      C.sub.10 reddish purple                                4-6       P.sub.6      C.sub.10 reddish purple                                4-7       P.sub.1      C.sub.11 red                                           4-8       P.sub.5      C.sub.11 reddish purple                                4-9       P.sub.6      C.sub.11 reddish purple                                4-10      P.sub.1      C.sub.12 pink                                          4-11      P.sub.5      C.sub.12 reddish purple                                4-12      P.sub.6      C.sub.12 reddish purple                                4-13      P.sub.1      C.sub.13 red                                           4-14      P.sub.2      C.sub.13 orange red                                    4-15      P.sub.3      C.sub.13 orange yellow                                 4-16      P.sub.4      C.sub.13 yellow                                        4-17      P.sub.5      C.sub.13 reddish purple                                4-18      P.sub.6      C.sub.13 reddish purple                                4-19      P.sub.6      C.sub.17 yellow                                        4-20      P.sub.6      C.sub.18 yellow                                        4-21      P.sub.5      C.sub.19 blue                                          4-22      P.sub.6      C.sub.19 blue                                          4-23      P.sub.5      C.sub.20 purple                                        4-24      P.sub.6      C.sub.20 purple                                        4-25      P.sub.1      C.sub.20 reddish purple                                4-26      P.sub.5      C.sub.21 reddish purple                                4-27      P.sub.6      C.sub.21 reddish purple                                4-28      P.sub.1      C.sub.21 red                                           ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                                    Product of the Invention                                                      4-1   4-7     4-13    4-14                                        ______________________________________                                        Color-developing                                                                            P.sub.1 P.sub.1 P.sub.1                                                                             P.sub.2                                   material                                                                      Coupling agent                                                                              C.sub.9 .sub. C.sub.11                                                                        .sub. C.sub.13                                                                      .sub. C.sub.13                            Dyed hair trace:                                                              Color tone    red     red     red   orange red                                Chroma        B       B       B     B                                         Color intensity                                                                             B       B       A     A                                         Dye stability for fading                                                                    A       A       A     A                                         ______________________________________                                    

While the invention has been described in detail and with reference tospecific examples thereof, it will be apparent to one skilled in the artthat various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A 2-alkyl-4-methoxy-5-aminophenol represented byformula (I) below or a salt thereof: ##STR11## wherein R¹ represents asubstituted or unsubstituted lower alkyl group.
 2. A2-alkyl-4-methoxy-5-nitrophenol derivative represented by formula (II):##STR12## wherein R¹ represents a substituted or unsubstituted loweralkyl group; and R² represents a hydrogen atom or a mesyl group.
 3. Adyeing composition for keratin fibers comprising a color-developingmaterial and said 2-alkyl-4-methoxy-5-aminophenol represented by formula(I) as claimed in claim 1 as a coupling agent.
 4. A dyeing compositionfor keratin fibers as claimed in claim 3, wherein said color-developingmaterial is the compound represented by formula (IX): ##STR13## whereinX represents hydrogen atom, a halogen atom, carboxyl group oracetylamino group.
 5. A 2-alkyl-4-methoxy-5-substituted aminophenolrepresented by formula (III) below or a salt thereof: ##STR14## whereinR¹ represents a substituted or unsubstituted lower alkyl group; R³represents a hydrogen atom, a substituted or unsubstituted lower alkylgroup or a substituted or unsubstituted hydorxyalkyl group; and R⁴represents a substituted or unsubstituted lower alkyl group, asubstituted or unsubstituted hydroxyalkyl group, a substituted orunsubstituted acetyl group, a substituted or unsubstituted benzoylgroup, or mesyl group.
 6. A 2-alkyl-4-methoxy-5-substituted aminophenolderivative represented by formula (IV): ##STR15## wherein R¹ representsa substituted or unsubstituted lower alkyl group; and R⁴ and R^(4'),which may be the same or different, each represents a substituted orunsubstituted lower alkyl group, a substituted or unsubstitutedhydroxyalkyl group, a substituted or unsubstituted acetyl group, asubstituted or unsubstituted benzoyl group, or mesyl group.
 7. A2-alkyl-4-methoxy-5-substituted aminophenol derivative represented byformula (V): ##STR16## wherein R¹ represents a substituted orunsubstituted lower alkyl group and n is an integer of 2 to
 4. 8. Adyeing composition for keratin fibers comprising a color-developingmaterial and said 2-alkyl-4-methoxy-5-substituted aminophenolrepresented by formula (III) as claimed in claim 5 as a coupling agent.9. A dyeing composition for keratin fibers as claimed in claim 8,wherein said color-developing material is the compound represented byformula (X): ##STR17## wherein R⁵ represents hydrogen atom, chlorineatom, methyl group, hydroxyethyl group or β-hydroxyethoxy group.
 10. Adyeing composition for keratin fibers as claimed in claim 8, whereinsaid color-developing material is the compound represented by formula(IX): ##STR18## wherein X represents hydrogen atom, a halogen atom,carboxyl group or acetylamino group.